CN114269795B - Method for purifying polyalkyl aluminoxane-containing solution using hydroxyl-containing compound and catalyst composition using the same - Google Patents
Method for purifying polyalkyl aluminoxane-containing solution using hydroxyl-containing compound and catalyst composition using the same Download PDFInfo
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- CN114269795B CN114269795B CN202080058203.XA CN202080058203A CN114269795B CN 114269795 B CN114269795 B CN 114269795B CN 202080058203 A CN202080058203 A CN 202080058203A CN 114269795 B CN114269795 B CN 114269795B
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- Prior art keywords
- containing solution
- catalyst composition
- compound
- trialkylaluminum
- aluminoxane
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 150000001875 compounds Chemical class 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229920000098 polyolefin Polymers 0.000 claims abstract description 23
- 150000003623 transition metal compounds Chemical class 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 29
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 28
- 150000002430 hydrocarbons Chemical class 0.000 claims description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 19
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 17
- -1 triisopropylaluminum Chemical compound 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 3
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 claims description 2
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 claims description 2
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 61
- 239000000243 solution Substances 0.000 description 76
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 37
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- 150000004645 aluminates Chemical class 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 10
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 10
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 8
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- DQVXWCCLFKMJTQ-UHFFFAOYSA-N (4-methylphenoxy)boronic acid Chemical compound CC1=CC=C(OB(O)O)C=C1 DQVXWCCLFKMJTQ-UHFFFAOYSA-N 0.000 description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 5
- HCIMXTXCDVBLOA-UHFFFAOYSA-N [4-(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC=C(C(F)(F)F)C=C1 HCIMXTXCDVBLOA-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 5
- 239000002516 radical scavenger Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- VIHLXRWXWPXIAY-UHFFFAOYSA-N 1,3,5-trihydroxycyclohexa-2,4-diene-1-carboxylic acid Chemical compound OC(=O)C1(O)CC(O)=CC(O)=C1 VIHLXRWXWPXIAY-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910010038 TiAl Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- TUCIXUDAQRPDCG-UHFFFAOYSA-N benzene-1,2-diol Chemical compound OC1=CC=CC=C1O.OC1=CC=CC=C1O TUCIXUDAQRPDCG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000012134 supernatant fraction Substances 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/602—Component covered by group C08F4/60 with an organo-aluminium compound
- C08F4/6028—Component covered by group C08F4/60 with an organo-aluminium compound with an alumoxane, i.e. a compound containing an -Al-O-Al-group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/06—Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
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Abstract
The present invention relates to a method for purifying a polyalkylaluminoxane-containing solution using a hydroxyl group-containing compound, a method for producing a catalyst composition using the method, a catalyst composition produced by the production method, and a method for producing an olefin polymer using the catalyst composition.
Description
Cross Reference to Related Applications
The present application claims the benefit of korean patent application No. 2019-011157 filed in the korean intellectual property office on the date of 9 and 30 of 2019, the disclosure of which is incorporated herein by reference in its entirety.
Technical Field
The present invention relates to a method for purifying a polyalkylaluminoxane-containing solution using a hydroxyl group-containing compound, a method for producing a catalyst composition using the method, a catalyst composition produced by the production method, and a method for producing an olefin polymer using the catalyst composition.
Background
It is well known that polyalkylaluminoxane compositions, which are partial hydrolysates of alkylaluminum, are used as cocatalysts or scavengers for activating procatalysts in the production of olefin polymers. The scavenger is a material added to the catalyst system to react with impurities present in the polymerization reactor, solvent, monomer feed, etc., and is used to prevent catalyst poisoning during polymerization of olefin monomers by reaction with impurities. Specifically, as the scavenger, various compounds such as trialkylaluminum, alkylaluminoxane, dialkylzinc, and dialkylmagnesium are used. As described above, polymethylaluminoxane, polyisobutylaluminoxane, or the like may be exemplified.
Polyalkylaluminoxanes are an example of scavengers that are commercially available as solutions in the state of being dissolved in hydrocarbon solvents such as toluene and can be purchased and used in polymerization reactions when desired. In this case, in addition to the polyalkylaluminoxane as a main component, commercially available polyalkylaluminoxane solutions contain Trimethylamine (TMA), triisobutylaluminum (Tibal), and the like. When it is directly used for polymerization, TMA and Tibal and the like cause a reaction with a transition metal compound as a main catalyst, thereby interfering with the production of an olefin polymer by reducing the catalytic activity of the transition metal compound, or disabling the production of a high molecular weight olefin polymer by participating in the polymerization and acting as a chain transfer agent.
As a typical method for removing impurities such as Tibal from a commercially available polyalkylaluminoxane solution, a method for preventing an additional reaction of Tibal is disclosed, in which a purchased composition solution is reacted with 2, 6-di-t-butyl-4-methylphenol (BHT) to combine BHT with aluminum element of Tibal.
However, although Tibal freely floating in solution can be removed by the above reaction, the product of Tibal binding to BHT is also soluble in the hydrocarbon solvent constituting the polyalkylaluminoxane composition and thus participates in the polymerization reaction. Thus, it is expected that additional problems may occur.
Therefore, there is a need to develop a method of: by maximizing the removal of TiAl present in commercially available polyaluminoxane solutions, the catalytic activity of transition metal compounds during polymerization of olefin monomers is enhanced without interfering with the ability of the polyaluminoxane to scavenge polar impurities or activate the catalyst and permanently remove Tibal from solution, thereby preventing the problem of Tibal from recovering floating in solution due to reverse reactions.
[ Prior art document ]
[ Patent document ]
KR 1996-0005169 B1
Disclosure of Invention
Technical problem
In one aspect of the present invention, a process is provided wherein a solution containing a polyalkylaluminoxane is reacted with a hydroxyl containing compound, the reaction product is filtered and purified, and the filtered and purified product is then mixed with a transition metal compound to prepare a catalyst composition.
Another aspect of the invention provides a catalyst composition using a polyalkyl aluminoxane containing solution containing a small amount of trialkylaluminum.
In yet another aspect, the present invention provides a process for producing an olefin polymer using the catalyst composition.
Technical proposal
According to one aspect of the present invention, there is provided a process for producing a catalyst composition, the process comprising: (S1) preparing a polyalkyl aluminoxane-containing solution comprising polyalkyl aluminoxane, trialkyl aluminum and a hydrocarbon solvent, (S2) reacting the polyalkyl aluminoxane-containing solution with a hydroxyl group-containing compound, (S3) filtering the reaction product of step (S2) and (S4) mixing the filtrate of step (S3) with a transition metal compound.
According to another aspect of the present invention, there is provided a catalyst composition comprising: a polyalkyl aluminoxane-containing solution having polyalkyl aluminoxane, trialkyl aluminum and a hydrocarbon solvent, and a transition metal compound, wherein the trialkyl aluminum is 4.3 mol% or less based on the polyalkyl aluminoxane-containing solution.
According to yet another aspect of the present invention, there is provided a process for producing an olefin polymer, the process comprising polymerizing an olefin monomer in the presence of the catalyst composition.
Advantageous effects
When commercially available solutions containing polyalkylaluminoxanes are purified according to the process of the present invention, trialkylaluminum present in the solution can be removed therefrom. When a polyalkylaluminoxane-containing solution from which trialkylaluminum is removed is used as a catalyst composition, there is an effect of preventing the polymerization reaction from being disturbed by trialkylaluminum and maximizing the activity of a main catalyst compound, thereby efficiently producing an olefin polymer.
In addition, since the insoluble solids produced have been physically removed from the catalyst composition of the present invention, there is no concern about the problem of reverse reaction. In addition, since a separate additive such as BHT is not required, there is an advantage in that only trialkylaluminum is easily removed from the solution and no separate residue remains in the solution, thereby obtaining a high purity olefin polymer.
Detailed Description
Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.
It should be understood that words or terms used in the specification and claims of the present invention should not be construed to have meanings defined in commonly used dictionaries. It will be further understood that words or terms should be interpreted to have meanings consistent with their meanings in the context of the relevant art and the technical concept of the present invention, based on the principle that the inventors can properly define the words or terms to best explain the invention.
[ Method of producing catalyst composition ]
The process for producing the catalyst composition of the present invention is characterized by comprising: (S1) preparing a polyalkyl aluminoxane-containing solution comprising polyalkyl aluminoxane, trialkyl aluminum and a hydrocarbon solvent, (S2) reacting the polyalkyl aluminoxane-containing solution with a hydroxyl group-containing compound, (S3) filtering the reaction product of step (S2); and (S4) mixing the filtrate of step (S3) with a transition metal compound.
Step (S1)
Step (S1) is a step of preparing a polyalkylaluminoxane-containing solution containing polyalkylaluminoxane, trialkylaluminum and a hydrocarbon solvent.
The preparation of the polyalkyl aluminoxane containing solution may be entirely included in the present invention regardless of the method or route by which the polyalkyl aluminoxane containing solution is obtained, but in particular, may refer to preparation by obtaining a commercially available polyalkyl aluminoxane containing solution. Currently, commercially available polyalkylaluminoxanes are sold in the form of a solution dissolved in a hydrocarbon solvent and contain a predetermined content of trialkylaluminum, and therefore, there is a problem of degrading the catalytic activity of the main catalyst when participating in polymerization. It is an object of the present invention to perform purification so as to effectively remove trialkylaluminum contained in the polyalkylaluminoxane containing solution prepared in step (S1), and thus, to more effectively use the trialkylaluminum-removed polyalkylaluminoxane containing solution in producing olefin polymers.
Polyalkylaluminoxanes may be added to the catalyst composition to act as a scavenger and/or promoter material.
The polyalkylaluminoxane may be one or more selected from the group consisting of polymethylaluminoxane, polyethylaluminoxane, polyisobutylaluminoxane, and polybutylaluminoxane, and may be, for example, polyisobutylaluminoxane, but is not limited thereto.
The trialkylaluminum may be one or more selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum and methyldiethylaluminum, and may be preferably triisobutylaluminum, but is not limited thereto.
The hydrocarbon solvent may be one or more selected from the group consisting of: an aliphatic hydrocarbon solvent including any one of pentane, hexane, heptane, nonane, decane, cyclohexane and isomers thereof, and an aromatic hydrocarbon solvent including any one of toluene, benzene, xylene and isomers thereof, and the like, and hexane may be preferable, but is not limited thereto.
Preferably, step (S1) may be a step of preparing a mixed solution comprising poly (isobutylaluminoxane), triisobutylaluminum and hexane.
The content of the hydrocarbon solvent contained in the polyalkylaluminoxane-containing solution may be 20 to 99% by weight based on the polyalkylaluminoxane-containing solution. When the content of the hydrocarbon solvent is less than 20% by weight, insoluble solids resulting from the reaction of the polyalkylaluminoxane-containing solution and the hydroxyl group-containing compound are entangled with each other as described below, and thus cannot be sufficiently stirred. Thus, it may be difficult to achieve the effect of the present invention, i.e., to remove trialkylaluminum from a polyalkylaluminoxane-containing solution. Therefore, a sufficient amount of hydrocarbon solvent is required.
Step (S2)
Step (S2) is a step of reacting a solution containing polyalkylaluminoxane with a hydroxyl group-containing compound.
The method of reacting the polyalkyl aluminoxane-containing solution with the hydroxyl group-containing compound may be performed by adding the hydroxyl group-containing compound to the polyalkyl aluminoxane-containing solution prepared in step (S1), for example, by transferring the hydroxyl group-containing compound in a slurry state to the polyalkyl aluminoxane-containing solution. Alternatively, the method may be carried out by adding a solution containing a polyalkylaluminoxane to a hydroxyl group containing compound. The mixing order or rate of the respective materials is not limited as long as the polyalkylaluminoxane-containing solution and the hydroxyl group-containing compound can be brought into contact with each other to react, and can be appropriately adjusted by those skilled in the art.
In step (S2), the trialkylaluminum and the hydroxyl group-containing compound are reacted in a mixed solution of a polyalkylaluminoxane-containing solution and a hydroxyl group-containing compound, thereby producing a solid product, and the solid product may be insoluble in a hydrocarbon solvent in the mixed solution.
Trialkylaluminum is a naturally flammable and water-blocking substance and is therefore classified as a three-stage hazardous substance, unlike trialkylaluminum, the insoluble solid is stable in air and is therefore a non-hazardous substance that does not burn or produce flammable materials. The production process of the present invention not only effectively removes trialkylaluminum but also converts dangerous trialkylaluminum to non-dangerous material and is therefore more preferable than a process of physically separating trialkylaluminum or aluminoxane itself.
In addition, the hydroxyl group-containing compound may be 100 equivalents or less based on 1 equivalent of trialkylaluminum contained in the polyalkylaluminoxane-containing solution. Specifically, the hydroxyl group-containing compound may be 0.01 equivalent to 100.00 equivalents based on 1 equivalent of trialkylaluminum contained in the polyalkylaluminoxane-containing solution, and may be used in an amount of 0.01 equivalent or more, 0.05 equivalent or more, 0.10 equivalent or more, 1.00 equivalent or more, 100.00 equivalent or less, 50.00 equivalent or less, or 10.00 equivalent or less.
When the hydroxyl group-containing compound is less than 0.01 equivalent, the reaction with trialkylaluminum may not be sufficiently achieved, and thus the effect of removing trialkylaluminum may not be significant. When the hydroxyl group-containing compound is more than 100 equivalents, the efficiency of removing trialkylaluminum does not increase in proportion to the amount of the hydroxyl group-containing compound used, and thus economic feasibility may be lowered. In addition, the amount of insoluble solids formed is excessive, so that they are entangled with each other, and it is difficult to stir and filter them.
By hydroxyl-containing compounds is meant compounds containing one or more hydroxyl groups, in particular C2-60 compounds containing two or more hydroxyl groups. Preferably, the hydroxyl-containing compound may be a C2-30 compound containing two or more hydroxyl groups. As described above, the hydroxyl group-containing compound containing two or more hydroxyl groups can react more effectively with trialkylaluminum, and thus can be preferably used.
Materials combined with trialkylaluminum are most likely to cure when the solubility of the hydroxyl-containing compound in organic solvents such as hexane is low. Therefore, the effect of the present invention can be more excellently achieved.
In this case, the hydroxyl group may replace a hydrogen atom on the aromatic ring, or may be coupled to a hydrocarbon chain. When two or more aromatic rings are present, the hydroxyl groups may each replace a hydrogen atom on a different aromatic ring, or may all replace a hydrogen atom on one aromatic ring, but the present invention is not limited thereto.
Specific examples of the hydroxyl group-containing compound may be one or more selected from the group consisting of 1,3, 5-trihydroxybenzene, neopentyl glycol, naphthalene-1, 5-diol, ethylene glycol, bisphenol a, catechol, methylhydroquinone, and 1,2, 3-trihydroxybenzene, but are not limited thereto.
Step (S3)
Step (S3) is a step of filtering the reaction product of step (S2), and is a step of filtering insoluble solids produced by the reaction of trialkylaluminum and hydroxyl group-containing compound in the previous step (S2) using a filter membrane, thereby removing insoluble solids from the mixed solution.
The filtration may be performed using a filter membrane having a pore size of 0.1 μm to 40.0 μm, in particular, a pore size of 0.10 μm or more, 0.15 μm or more, 0.20 μm or more, 1.0 μm or more, 5.0 μm or more, 7.0 μm or more, 40.0 μm or less, 35.0 μm or less, 30.0 μm or less, 20.0 μm or less, 15.0 μm or less, or, for example, 10 μm.
When the pore diameter of the filter membrane is less than 0.1 μm, there may be a problem in that insoluble solids produced by the reaction of trialkylaluminum with hydroxyl-containing compounds may clog the pores of the filter membrane, thereby reducing the filtration efficiency and extending the filtration time. When the pore size of the filter membrane is greater than 40.0. Mu.m, the insoluble solids pass through the filter membrane, resulting in failure to separate and remove the insoluble solids.
In the present invention, a filter membrane having a pore size within a range that allows for efficient removal of the solids produced in step (S2) may be appropriately selected and used. As a result, a high purity polyalkylaluminoxane-containing solution from which trialkylaluminum is effectively removed can be obtained.
In step (S3), the reaction product of step (2) may be immediately filtered, or the reaction product of step (2) may be left to stand to precipitate insoluble solids, and then only the supernatant may be recovered and filtered. Only the supernatant may be recovered and filtered as described above to mainly remove a large amount of insoluble solids, and thus, the efficiency of removing insoluble solids may be improved.
As described above, the method of producing a catalyst composition of the present invention physically removes trialkylaluminum contained in a polyalkylaluminoxane-containing solution through steps (S1) to (S3) so that the trialkylaluminum in the solution can be reduced to 4.3 mol% or less and the content of trialkylaluminum can be further reduced according to reaction conditions, the type of polyalkylaluminoxane and trialkylaluminum, the pore size of a filtration membrane, etc.
Step (S4)
Step (S4) is a step of mixing the filtrate of step (S3) with a transition metal compound.
As described above, in the present invention, a solution in which the relative content of polyalkylaluminoxane is increased and the content of impurities such as trialkylaluminum is reduced is obtained by steps (S1) to (S3). In addition, through the step (S4), the catalyst composition is prepared by mixing a transition metal compound serving as a main catalyst. The catalyst composition prepared as described above comprises polyalkylaluminoxane, which is used as a scavenger and/or a cocatalyst while being free from the interference of trialkylaluminum, and thus the catalytic activity of the transition metal compound can be significantly improved.
[ Catalyst composition ]
The catalyst composition of the present invention comprises: a polyalkyl aluminoxane-containing solution comprising polyalkyl aluminoxane, trialkyl aluminum and a hydrocarbon solvent, and a transition metal compound, wherein the trialkyl aluminum is 4.3 mole% or less based on the polyalkyl aluminoxane-containing solution.
The catalyst composition can be obtained by the production process of the present invention. According to the present invention, the catalyst composition is prepared by removing trialkylaluminum from a polyalkyl-containing aluminoxane solution and mixing the trialkylaluminum-removed polyalkyl-containing aluminoxane solution with a transition metal compound. The trialkylaluminum content contained in the polyalkylaluminoxane-containing solution is as low as 4.3 mole percent or less.
As described above, the catalyst composition comprises a polyalkylaluminoxane and a transition metal compound (procatalyst compound), and may further comprise one or more cocatalyst compounds. At this time, the catalyst composition may refer to a state in which three components of the transition metal compound, the cocatalyst compound, and the polyalkylaluminoxane are mixed simultaneously or in any order to obtain components as a composition having activity.
As the transition metal compound, any compound known to be capable of functioning as a catalyst in the polymerization reaction of olefin monomers can be used.
The cocatalyst may include one or more selected from the following formula 1 or formula 2, but the present invention is not limited thereto.
[ 1]
D(R1)3
In the above formula 1, D is boron, and R 1 are each independently a halogen radical, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms.
[ 2]
[ L-H ] +[Z(A)4]- or [ L ] +[Z(A)4]-
In the above formula 2, L is a neutral or cationic lewis acid, H is a hydrogen atom, Z is a group 13 element, a is each independently an aryl group having 6 to 20 carbon atoms (in which one or more hydrogen atoms may be substituted) or an alkyl group having 1 to 20 carbon atoms (in which one or more hydrogen atoms may be substituted) and a substituent is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.
The compound represented by formula 1 above may include trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, but is not limited thereto.
Examples of the compound represented by the above formula 2 may include trimethylammonium tetraphenyl borate, triethylammonium tetraphenyl borate, tripropylammonium tetraphenyl borate, tributylammonium tetraphenyl borate, trimethylammonium tetrakis (p-tolyl) borate, triethylammonium tetrakis (p-tolyl) borate, tripropylammonium tetrakis (p-tolyl) borate, tributylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o, p-dimethylphenyl) borate, triethylammonium tetrakis (o, p-dimethylphenyl) borate, tripropylammonium tetrakis (o, para-dimethylphenyl) borate, tributylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (p-trifluoromethylphenyl) borate, triethylammonium tetrakis (p-trifluoromethylphenyl) borate, tripropylammonium tetrakis (p-trifluoromethylphenyl) borate, tributylammonium tetrakis (p-trifluoromethylphenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, N-diethylaniline tetraphenyl borate, N-diethylaniline tetrakis (pentafluorophenyl) borate, diethylammonium tetrakis (pentafluorophenyl) borate, trimethylphosphonium tetraphenyl borate, triphenylphosphonium tetraphenyl borate, triphenylcarbonium tetrakis (p-trifluoromethylphenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, trimethylammonium tetraphenyl aluminate, triethylammonium tetraphenyl aluminate, tripropylammonium tetraphenyl aluminate, tributylammonium tetraphenyl aluminate, trimethylammonium tetrakis (p-tolyl) aluminate, triethylammonium tetrakis (p-tolyl) aluminate, tripropylammonium tetrakis (p-tolyl) aluminate, tributylammonium tetrakis (p-tolyl) aluminate, trimethylammonium tetrakis (o, p-dimethylphenyl) aluminate, triethylammonium tetrakis (o, p-dimethylphenyl) aluminate, tripropylammonium tetrakis (o, p-dimethylphenyl) aluminate, tributylammonium tetrakis (p-tolyl) aluminate, trimethylammonium tetrakis (p-trifluoromethylphenyl) aluminate, triethylammonium tetrakis (p-trifluoromethylphenyl) aluminate, tripropylammonium tetrakis (p-trifluoromethylphenyl) aluminate, tributylammonium tetrakis (p-trifluoromethylphenyl) aluminate, trimethylammonium tetrakis (pentafluorophenyl) aluminate, triethylammonium tetrakis (pentafluorophenyl) aluminate, tripropylammonium tetrakis (pentafluorophenyl) aluminate, tributylammonium tetrakis (pentafluorophenyl) aluminate, N-diethylaniline, N-difluoroaniline, and the like, but not limited thereto.
The catalyst composition may be produced by a production method comprising contacting a transition metal compound with a compound represented by the above formula 1 to obtain a mixture, and adding the compound represented by the formula 2 to the mixture.
At this time, the molar ratio of the compound represented by formula 1 to the transition metal compound may be 1:2 to 1:5,000, preferably 1:10 to 1:1,000, and more preferably 1:20 to 1:500.
When the molar ratio of the compound represented by formula 1 to the transition metal compound is less than 1:2, the amount of alkylating agent is very small, and thus there is a problem in that the alkylation of the metal compound is not completely achieved. When it is more than 1:5,000, alkylation of the metal compound is achieved, but there is a problem in that activation of the alkylated metal compound cannot be completely achieved due to side reaction between the remaining excessive alkylating agent and the activator (i.e., the compound represented by the above formula 2).
In addition, the catalyst composition may be produced by a production method comprising contacting a transition metal compound with a compound represented by the above formula 2.
At this time, the molar ratio of the compound represented by formula 2 to the transition metal compound may be 1:1 to 1:25, preferably 1:1 to 1:10, and more preferably 1:1 to 1:5.
When the molar ratio of the compound represented by formula 2 to the transition metal compound is less than 1:1, the amount of the alkylating agent is relatively small, and thus there is a problem in that the alkylation of the metal compound is not completely achieved, thereby decreasing the activity of the catalyst composition. When it is more than 1:25, the activation of the transition metal compound is completely achieved, but there is a problem in that the unit cost of the catalyst composition is uneconomical or the purity of the produced polymer is poor due to the excessive amount of the activator remaining.
When the catalyst composition is produced, a hydrocarbon-based solvent (e.g., pentane, hexane, heptane, etc.) or an aromatic solvent (e.g., benzene, toluene, etc.) may be used as the reaction solvent, but the present invention is not necessarily limited thereto. All solvents useful in the art can be used.
The polyalkyl aluminum content of the polyalkyl aluminoxane containing solution contained in the catalyst composition is relatively low and thus can be used as a scavenger and/or cocatalyst in the production of olefin polymers. Accordingly, the catalyst composition provided in the present invention has excellent activity to promote polymerization reaction, and thus olefin polymers can be produced in good yields using the catalyst composition.
In addition, since the trialkylaluminum is converted to a solid product and filtered, it is permanently removed from the polyalkylaluminoxane containing solution, so that there is no risk of a reverse reaction taking place, so that the trialkylaluminum again appears in the solution. Thus, the stability and predictability of the polymerization reaction can be further improved.
[ Process for producing olefin Polymer ]
The process for producing an olefin polymer of the present invention is characterized by comprising polymerizing an olefin monomer in the presence of a catalyst composition.
The term "polymer" refers to a polymeric compound produced by polymerizing the same or different types of monomers. Thus, the generic term "polymer" includes the term "homopolymer", which is generally used to refer to polymers produced from a single type of monomer, as well as the term "interpolymer", as defined below.
The olefin monomer may be one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene, but is not limited thereto.
In particular, the olefin polymer of the present invention may be an olefin homopolymer, an olefin/α -olefin copolymer, and preferably an ethylene/α -olefin copolymer, depending on the type of olefin-based monomer. In this case, the content of the α -olefin-based monomer (comonomer) may be appropriately selected by those skilled in the art according to the purpose and use of the olefin polymer, and may be about 1 to 99 mol%.
The most preferred polymer production process using the catalyst composition is a solution process. However, when used with an inorganic support (e.g., silica), the catalyst composition may be applied to slurry or gas phase processes.
The catalyst composition may be injected after dissolution or dilution in the following solvents: aliphatic hydrocarbon solvents having 5 to 12 carbon atoms and suitable for use in the polymerization process of olefin monomers (e.g., pentane, hexane, heptane, nonane, decane and isomers thereof), aromatic hydrocarbon solvents (e.g., toluene and benzene), and hydrocarbon solvents substituted with chlorine atoms (e.g., methylene chloride and chlorobenzene). The solvent used herein is preferably used after removing a small amount of water or air (which acts as a catalyst poison) by treatment with a small amount of aluminum alkyl. In addition to the catalyst composition, another cocatalyst may be used.
Examples
Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
[ Preparation of reagents ]
Poly (isobutylaluminoxane) was purchased from Tosho Co., ltd, dissolved in hexane and used. The polyisobutylaluminoxane containing solution purchased from Tosho co., ltd. Contains 4.4 mol% triisobutylaluminum. Hydroxyl containing compounds were purchased from Aldrich co., ltd.
[ Preparation and purification of a solution containing Poly (isobutyl aluminoxane) ]
Production example 1
2.00 Equivalents of 1,3, 5-trihydroxybenzene (based on 1 equivalent of triisobutylaluminum contained in the polyisobutylaluminum-containing solution) were added to a 500mL schlenk bottle, and dried in vacuo for 3 hours. 175g of the polyisobutylaluminoxane containing solution and 175g of hexane were added to another 500mL schlenk flask and prepared.
The 1,3, 5-trihydroxybenzene prepared in the 500mL schlenk flask described above was all transferred as a slurry to the 500mL schlenk flask through a cannula using 30mL hexane, in which a solution containing poly-isobutylaluminoxane and hexane were contained.
After the movement was completed, the mixture was stirred for 12 hours, allowed to stand to form a solid product, and then allowed to stand overnight. When it was left to stand, the supernatant fraction was carefully filtered using a filter having a pore size of 10.0. Mu.m.
Production examples 2 to 11
A solution containing polyisobutylaluminoxane was prepared in the same manner in example 1 except that the modifications shown in the following Table 1 were made.
Comparative production example 1
The polyalkylaluminoxane-containing solution was purchased from Tosho co., ltd. And used as such.
TABLE 1
Hydroxyl group-containing compound | Equivalent based on 1 equivalent of triisobutylaluminum | Aperture (mum) | |
Production example 1 | 1,3, 5-Trihydroxybenzene | 2.00 | 10.00 |
Production example 2 | 1,3, 5-Trihydroxybenzene | 0.05 | 10.00 |
Production example 3 | 1,3, 5-Trihydroxybenzene | 2.00 | 0.15 |
Production example 4 | 1,3, 5-Trihydroxybenzene | 3.00 | 35.00 |
Production example 5 | Neopentyl glycol | 4.00 | 10.00 |
Production example 6 | Naphthalene-1, 5-diol | 4.00 | 10.00 |
Production example 7 | Ethylene glycol | 6.60 | 10.00 |
Production example 8 | Bisphenol-A | 4.00 | 10.00 |
Production example 9 | Catechol (catechol) | 2.00 | 10.00 |
Production example 10 | Methyl hydroquinone | 4.00 | 10.00 |
Production example 11 | 1,2, 3-Trihydroxybenzene | 2.00 | 10.00 |
Comparative production example 1 | - | - | 10.00 |
Experimental example 1
(1) Triisobutylaluminum (mole%)
The solution obtained by performing the above filtration was dissolved in THF deuteration solvent by 1 H NMR, and the content of the remaining triisobutylaluminum was measured.
(2) Filtration time (hours)
The time until the filter input has all passed through the filter is measured.
(3) Recovery (%)
Recovery (%) = solution containing polyisobutylaluminoxane (g) recovered after filtration/solution containing polyisobutylaluminoxane (g) x100 in reactant state
TABLE 2
Triisobutylaluminum (mole%) | Filtration time (hours) | Recovery (%) | |
Production example 1 | <0.1 | 0.1 | 94 |
Production example 2 | 2.900 | 0.1 | 95 |
Production example 3 | <0.1 | 24.0 | 90 |
Production example 4 | <0.1 | 0.1 | 95 |
Production example 5 | <0.1 | 0.1 | 90 |
Production example 6 | 1.176 | 0.1 | 90 |
Production example 7 | 0.137 | 0.1 | 90 |
Production example 8 | 1.470 | 0.1 | 90 |
Production example 9 | <0.1 | 0.1 | 90 |
Production example 10 | <0.1 | 0.1 | 90 |
Production example 11 | 0.176 | 0.1 | 90 |
Comparative production example 1 | 4.400 | - | - |
As shown in table 2 above, in all production examples 1 to 11 prepared by reacting a polyalkylaluminoxane-containing solution with a hydroxyl group-containing compound and then filtering according to the present invention, triisobutylaluminum was largely removed, and thus, it can be seen that the content of remaining triisobutylaluminum was much lower than that of comparative production example 1.
More specifically, in the case of production example 1 (in which 2.00 equivalents of 1,3, 5-trihydroxybenzoic acid was used based on 1.00 equivalents of triisobutylaluminum and a filter membrane having a pore size of 10.0 μm was used), triisobutylaluminum was selectively removed in a short period of time, and thus the filtration time was shortened and the recovery rate was excellent.
Meanwhile, in the case of production example 2 using 0.05 equivalent of 1,3, 5-trihydroxybenzene based on 1.00 equivalent of triisobutylaluminum, the effect of removing triisobutylaluminum based on 1.00 equivalent of triisobutylaluminum is relatively reduced.
In addition, in production example 3 using a filter membrane having a pore size of 0.15 μm, the filtration time was increased; in production example 4 using a filter membrane with a pore size of 35.0 μm, some insoluble solids were observed to be filtered as well.
[ Production of olefin Polymer ]
Example 1
The transition metal compound of the following formula a was prepared using the production method disclosed in korean patent registration No. 10-0738694.
[ A ]
Hexane solvent (900 mL) and 1-octene (300 mL) were charged to a 2L autoclave continuous process reactor, which was then preheated to 150 ℃. Thereafter, ethylene was added to the autoclave continuous process reactor to set the pressure in the reactor to 35 bar, and then 1. Mu. Mol of a transition metal compound, 10 equivalents of dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst, 1.5mmol of the polyisobutylaluminum-containing solution produced in production example 1 were simultaneously added to the reactor. The copolymer was prepared by holding for 8 minutes and continuously conducting the copolymerization reaction. Next, the remaining ethylene gas was removed, and an excessive amount of ethanol was added to the obtained copolymer-containing solution to induce precipitation. The precipitated polymer was washed with ethanol two to three times and then dried in a vacuum oven at 90 ℃ for more than 12 hours to obtain a copolymer.
Example 2
The transition metal compound of the following formula B was prepared using the production method disclosed in korean patent registration No. 10-2016-0019875.
[ B ]
An olefin polymer was produced in the same manner as in example 1, except that the above-mentioned compound of formula B was used as the transition metal compound.
Comparative example 1
An olefin polymer was produced in the same manner as in example 1, except that the polyalkyl aluminoxane containing solution of comparative production example 1 was used in place of the polyalkyl aluminoxane containing solution of production example 1.
Comparative example 2
An olefin polymer was produced in the same manner as in example 2, except that the polyalkyl aluminoxane containing solution of comparative production example 1 was used in place of the polyalkyl aluminoxane containing solution of production example 1.
Table 2 below summarizes the types of transition metal compounds and polyalkylaluminoxane-containing solutions used in examples 1 and 2 and comparative examples 1 and 2.
TABLE 3
Transition metal compound | Solutions containing polyalkylaluminoxanes | |
Example 1 | [ A ] | Production example 1 |
Example 2 | [ B ] | Production example 1 |
Comparative example 1 | [ A ] | Comparative production example 1 |
Comparative example 2 | [ B ] | Comparative production example 1 |
[ Analysis of physical Properties of olefin Polymer ]
Experimental example 1
The physical properties of the polymers produced in each of the examples and comparative examples were compared and analyzed. The measurement conditions and methods are as follows, and the measurement results are summarized in table 3 below.
(1) Catalytic Activity (KgPE/mmol)
The catalyst activity is calculated by dividing the resulting polymer by the moles of transition metal compound used in the polymerization reaction.
(2) Melt index (MI 2.16)
Melt index was measured according to ASTM D-1238 (condition E,190 ℃,2.16Kg load).
(3) Density (g/cc)
A sheet having a thickness of 3mm and a radius of 2cm was produced as a sample at 180℃using a press die according to ASTM D-792, and then cooled at a rate of 10℃per minute. The density was measured using a Mettler scale.
(4) Melting temperature (T m, DEG C)
The melting temperature of the polymer was measured using a differential scanning calorimeter (DSC, apparatus name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 150℃and then held for 5 minutes. The temperature of the polymer was reduced to-100℃and then again increased. At this time, the temperature rise rate and the temperature decrease rate were adjusted to 10℃per minute, respectively. The melting temperature is determined as the maximum point of the endothermic peak measured during the second temperature increase interval.
(5) Crystallization temperature (T c, DEG C)
The crystallization temperature was determined as the maximum point of the exothermic peak in the curve that appears when the temperature was lowered, using the same method as measuring the melting temperature using DSC.
TABLE 4
As can be seen from the results of table 3 above, in the case of examples 1 and 2 using the catalyst composition produced according to the present invention, the catalyst activity as a whole was significantly increased as compared with the comparative example.
Specifically, when comparing example 1 and comparative example 1 and example 2, which have the same type of transition metal compound, even though the transition metal compound is the same, the catalyst activity of examples 1 and 2, in which triisobutylaluminum was removed, was three times higher than that of comparative examples 1 and 2, respectively, by reacting a solution containing polyisobutylaluminum with a hydroxyl group-containing compound.
As described above, the catalyst composition produced by the production method of the present invention can enhance the catalytic activity of the transition metal compound and effectively produce olefin polymers, which has been confirmed to be an effect that can be achieved in various transition metal compounds, irrespective of the type of transition metal compound.
Claims (11)
1. A process for producing a catalyst composition, the process comprising:
(S1) preparing a polyalkyl aluminoxane containing solution comprising polyalkyl aluminoxane, trialkyl aluminum and a hydrocarbon solvent;
(S2) reacting the polyalkyl aluminoxane containing solution with a hydroxyl group-containing compound and forming a solid insoluble in the hydrocarbon solvent by the reaction of the trialkyl aluminum with the hydroxyl group-containing compound, wherein the hydroxyl group-containing compound is 0.05 equivalent to 100.00 equivalents based on 1 equivalent of trialkyl aluminum contained in the polyalkyl aluminoxane containing solution;
(S3) filtering the reaction product of step (S2) to remove insoluble solids from the solution, wherein the filtering is performed using a filter membrane having a pore size of 0.1 μm to 40.0 μm; and
(S4) mixing the filtrate of the step (S3) with a transition metal compound,
Wherein the hydroxyl-containing compound is a C2-60 compound containing two or more hydroxyl groups.
2. The method of claim 1, wherein the polyalkyl aluminoxane is one or more selected from the group consisting of polymethylaluminoxane, polyethylaluminoxane, and polybutylaluminoxane.
3. The method of claim 1, wherein the polyalkyl aluminoxane is a polyisobutyl aluminoxane.
4. The method of claim 1, wherein the trialkylaluminum is one or more selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tricyclopentylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, and methyldiethylaluminum.
5. The method of claim 1, wherein the trialkylaluminum is one or more selected from the group consisting of triisobutylaluminum, triisopropylaluminum, tri-sec-butylaluminum and triisopentylaluminum.
6. The method of claim 1, wherein the hydrocarbon solvent is 20 wt% to 99 wt% based on the polyalkylaluminoxane containing solution.
7. The method of claim 1, wherein the hydroxyl-containing compound is from 0.05 equivalents to 50.00 equivalents based on 1 equivalent of trialkylaluminum contained in the polyalkylaluminoxane-containing solution.
8. The method of claim 1, wherein the filtering of step (S3) is performed using a filter membrane having a pore size of 0.15 μm to 35.0 μm.
9. The method of claim 1, wherein step (S3) is performed by: allowing the reaction product of step (S2) to stand, and then recovering and filtering the supernatant therefrom.
10. A catalyst composition produced by the method of any one of claims 1 to 9 and comprising:
a polyalkyl aluminoxane containing solution comprising polyalkyl aluminoxane, trialkyl aluminum, and a hydrocarbon solvent; and
A transition metal compound which is a metal compound,
Wherein the trialkylaluminum is 2.9 mole percent or less based on the polyalkylaluminoxane containing solution.
11. A process for producing an olefin polymer, the process comprising polymerizing an olefin monomer in the presence of the catalyst composition of claim 10.
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US5831109A (en) * | 1995-12-22 | 1998-11-03 | Akzo Nobel Nv | Polyalkylaluminoxane compositions formed by non-hydrolytic means |
GB0220681D0 (en) * | 2002-09-05 | 2002-10-16 | Borealis Tech Oy | Process |
WO2010055652A1 (en) * | 2008-11-11 | 2010-05-20 | 東ソー・ファインケム株式会社 | Solid polymethylaluminoxane composition and process for producing same |
JP6063449B2 (en) * | 2012-03-28 | 2017-01-18 | 東ソー・ファインケム株式会社 | Method for producing small particle size solid polymethylaluminoxane composition |
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An Alternative Method for the Preparation of rialkylaluminum-Depleted Modified ethylaluminoxane (dMMAO);Ryo Tanaka等;Macromolecules;20170720;第50卷;5989−5993 * |
Dario Romano等.Aluminoxane co-catalysts for the activation of a bis phenoxyimine titanium (IV) catalyst in the synthesis of disentangled ultra-high molecular weight polyethylene.Polymer.2015,第74卷76-85. * |
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